JP6980205B2 - Hydrogen production catalyst and its production method, and hydrogen production equipment - Google Patents

Description

The present invention relates to a catalyst for hydrogen production, a method for producing the same, and a hydrogen production apparatus.

Hydrogen, which is a fuel for a fuel cell, is produced by a steam reforming reaction, for example, by reacting methane gas with steam at a high temperature. In recent years, small hydrogen production devices have been developed for the widespread use of fuel cell vehicles, and at the same time, there is a demand for hydrogen production catalysts that exhibit high catalytic activity even in a low temperature range.

The metal honeycomb catalyst used in the steam reforming reaction has features such as smaller pressure loss, less generation of hot spots, and excellent heat transferability than the pellet catalysts commonly used in the past. Therefore, a metal honeycomb catalyst with lower cost and higher efficiency has been developed. Non-Patent Document 1 describes a honeycomb catalyst for hydrogen production using a nickel foil.

Appl. Catal. A: General 507 (2015) 162-168

However, the pure nickel foil honeycomb catalyst of Non-Patent Document 1 exhibits low catalytic activity in a low temperature region, and therefore has a problem that it is difficult to apply it to a small hydrogen production apparatus.

In view of the above circumstances, an object of the present invention is to provide a hydrogen production catalyst exhibiting high catalytic activity even in a low temperature region, a production method thereof, and a hydrogen production apparatus using the same.

In order to achieve the above object, the catalyst for hydrogen production according to one embodiment of the present invention includes a metal foil and a metal active layer made of metal particles supported on the metal foil.
With this configuration, high catalytic activity can be obtained even in a low temperature region.

The metal active layer may contain a first element selected from Ni, Ru, Rh, Pt, Pd, Ir, Fe, and Co.

The first element may be Ni or Ru.

The metal active layer is selected from one or more of Ru, Re, Mn, Mo, W, Cr, Ta, Hf, Os, Sn, Zn, La, Ce, Rh, Pt, Mg, Al, Si, and Cu. It may further contain a second element different from the first element.
With this configuration, even higher catalytic activity can be obtained even in a low temperature region.

The second element may be selected from Re and Ru.
With this configuration, a catalyst for hydrogen production having excellent heat resistance can be obtained.

The metal particles are formed of an alloy containing the first element and the second element, and the content of the first element in the metal particles is 1 wt% or more and less than 100 wt%, and the first element in the metal particles. The content of the two elements may be more than 0 wt% and 99 wt% or less.

The content of the first element in the metal particles may be 30 wt% or more and 92 wt% or less, and the content of the second element in the metal particles may be 8 wt% or more and 70 wt% or less.

The metal foil may be mainly composed of a material selected from the group consisting of Ni, stainless steel, and iron-based alloys.

The metal foil may contain Ni as a main component.

The metal foil may form a honeycomb structure or a spiral structure.

The particle size of the metal particles may be 1 nm or more and 500 nm or less.

The particle size of the metal particles may be 10 nm or more and 150 nm or less.

The method for producing a catalyst for hydrogen production according to one embodiment of the present invention forms a strong acid powder layer containing a metal element on the surface of a metal foil. By thermally decomposing the strong acid powder layer, an oxide particle layer containing the metal element is formed. By reducing the oxide particle layer, a metal active layer containing the metal element is formed.
With this configuration, high catalytic activity can be obtained even in a low temperature region.

The strong acid powder layer may be formed by using the strong acid aqueous solution of the metal element.

The metal element may contain a first element selected from Ni, Ru, Rh, Pt, Pd, Ir, Fe, and Co.

The metal foil may contain the metal element as a main component and may form the strong acid powder layer by acid-treating the surface of the metal foil.

The metal element may be Ni.

The surface of the metal foil may be acid-treated with nitric acid.

The strong acid powder layer, the oxide particle layer, and the metal active layer may further contain a second element different from the first element as the metal element.

Even if one or more of the second elements are selected from Ru, Re, Mn, Mo, W, Cr, Ta, Hf, Os, Sn, Zn, La, Ce, Rh, Pt, Mg, Al, Si, and Cu. good.
With this configuration, even higher catalytic activity can be obtained even in a low temperature region.

The hydrogen production apparatus according to one embodiment of the present invention includes a supply unit for supplying a hydrogen raw material gas containing a hydrocarbon compound and a reaction gas containing steam, and the hydrogen raw material gas supplied from the supply unit and the above. It includes a catalytic reaction unit that reacts with a reaction gas to generate a steam reforming reaction, and the catalytic reaction unit has the hydrogen production catalyst.
With this configuration, high catalytic activity can be obtained even in a low temperature region.

It is possible to provide a hydrogen production catalyst and a method for producing the same, and a hydrogen production apparatus, which exhibit high catalytic activity even in a low temperature region.
More specifically, according to the catalyst for hydrogen production of the present invention, a metal foil and a metal active layer made of metal particles supported on the surface thereof are provided, whereby the specific surface area is increased and the temperature is as low as 1173 K or less. High catalytic activity can be exhibited even in the region. According to the production method of the present invention, the catalyst for hydrogen production of the present invention can be produced without using a special device or technique. Further, since the catalyst for hydrogen production of the present invention can exhibit high catalytic activity even in a small amount, the hydrogen production apparatus can be miniaturized.

It is a perspective view of the catalyst for hydrogen production which concerns on one Embodiment of this invention. It is a partial cross-sectional view showing an enlarged cross section of the said catalyst for hydrogen production. It is a flowchart which shows the manufacturing method A1 of the said catalyst for hydrogen production. It is a figure which shows an example of the manufacturing process of the substrate of the said catalyst for hydrogen production. It is a schematic diagram which shows an example of the substrate of the said catalyst for hydrogen production. It is a flowchart which shows the manufacturing method B1 of the said catalyst for hydrogen production. It is a schematic diagram of the hydrogen production apparatus using the said catalyst for hydrogen production. It is an SEM image which imaged the fine structure of the surface of the catalyst for hydrogen production in an Example. It is a graph which shows the catalyst property by the temperature rise experiment of the catalyst for hydrogen production in an Example. It is a graph which shows the catalyst property by the temperature rise experiment of the catalyst for hydrogen production in an Example. It is an SEM image which imaged the fine structure of the surface before the reduction treatment of the catalyst for hydrogen production in an Example. It is an SEM image which imaged the fine structure of the surface before the reduction treatment of the catalyst for hydrogen production in an Example. It is a graph which shows the catalyst property by the temperature rise experiment of the catalyst for hydrogen production in an Example.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

[Catalyst for hydrogen production 10]
(overall structure)
FIG. 1 is a perspective view of a hydrogen production catalyst 10 according to an embodiment of the present invention.
FIG. 2 is a partial cross-sectional view showing an enlarged cross section of the hydrogen production catalyst 10 of FIG.
The hydrogen production catalyst 10 in the present invention is a catalyst that produces hydrogen by a steam reforming reaction using a hydrogen raw material gas and steam.

The hydrogen production catalyst 10 has a substrate 11 and a metal active layer 12.

The substrate 11 is formed by winding a flat plate-shaped metal foil 11a and a wavy metal foil 11b integrally. As a result, the substrate 11 is configured as a columnar honeycomb structure having a flow path formed along the central axis direction thereof. Although it is shown in a columnar shape in FIG. 1, it may be wound depending on the shape of the reaction tube in which the hydrogen production catalyst 10 such as a prism or a polygonal casting is installed.

The metal active layer 12 is supported on the surface of the substrate 11. The metal active layer 12 functions as a catalyst for the steam reforming reaction. Note that FIG. 2 shows a state in which the metal foils 11a and 11b are not wound for convenience of explanation.

Since the substrate 11 is a honeycomb structure, the hydrogen production catalyst 10 can allow a gas such as a hydrogen raw material gas or water vapor to pass along the flow path of the substrate 11.
Further, the hydrogen production catalyst 10 can exhibit good catalytic activity when the metal active layer 12 formed in the honeycomb structure having a large surface area comes into contact with the gas. Further, the hydrogen production catalyst 10 can efficiently generate hydrogen by passing the gas through the honeycomb structure having a low pressure loss.

(Details of the substrate 11)
The metal foils 11a and 11b preferably contain, for example, any one of Ni, stainless steel, and an iron-based alloy as a main component. As a result, the metal active layer 12 is well supported on the metal foils 11a and 11b.
In particular, it is more preferable that the metal foils 11a and 11b contain Ni as a main component. High catalytic activity can be obtained by the Ni itself constituting the metal foils 11a and 11b acting as a catalyst.
Here, the main component means a component having a content of 50 wt% or more and 100 wt% or less in the metal foils 11a and 11b.

The thickness of the metal foils 11a and 11b may be, for example, several tens of μm, may be several hundred μm to several hundred μm, and is not limited thereto.

The substrate 11 is not limited to the honeycomb structure, and may be a spiral structure in which only the flat metal foil 11a is wound without using the wavy metal foil 11b.
The substrate 11 is made by winding the metal foils 11a and 11b, but may be made by another method.

(Details of the metal active layer 12)
The metal active layer 12 is made of metal fine particles supported on the surface of the substrate 11.
Since the metal active layer 12 is made of metal fine particles, the surface area of the hydrogen production catalyst 10 is increased. Therefore, the hydrogen production catalyst 10 can exhibit high catalytic activity even in a low temperature region of 1173 K or less. Further, the hydrogen production catalyst 10 can exhibit high catalytic activity even in a small amount.

The metal fine particles are finely divided metal particles having a particle size of 1 μm or less. In the metal active layer 12, the particle size of the metal fine particles is preferably 1 nm or more and 500 nm or less, more preferably 10 nm or more and 150 nm or less, and further preferably 50 nm or more and 150 nm or less. In the present specification, the particle size is calculated based on, for example, an image of a scanning electron microscope (SEM).
By setting the particle size to 500 nm or less, the surface area of the hydrogen production catalyst 10 can be made larger, and particularly high catalytic activity can be obtained even in a low temperature region. By setting the particle size to 1 nm or more, stable catalytic properties can be easily obtained.

The metal fine particles contain at least one or more of the transition metal elements of groups 4 to 11. The metal fine particles preferably contain a first element selected from Ni, Ru, Rh, Pt, Pd, Ir, Fe, and Co, and more preferably Ni or Ru. This results in higher catalytic activity even in the lower temperature range. In addition, high catalytic activity can be maintained for a long time.

Further, the metal fine particles are selected from one or more of Ru, Re, Mn, Mo, W, Cr, Ta, Hf, Os, Sn, Zn, La, Ce, Rh, Pt, Mg, Al, Si, and Cu. It is preferable to further contain a second element different from the first element. Further, it is more preferable that the second element is selected from Re and Ru. As a result, even higher catalytic activity can be obtained even in a low temperature region. In addition, high catalytic activity can be maintained for a longer period of time.

Further, the metal fine particles are formed of an alloy containing the first element and the second element.
The content of the first element in the metal fine particles is preferably 1 wt% or more and less than 100 wt%, and the content of the second element in the metal fine particles is preferably more than 0 wt% and 99 wt% or less.
It is more preferable that the content of the first element in the metal fine particles is 30 wt% or more and 92 wt% or less, and the content of the second element in the metal fine particles is 8 wt% or more and 70 wt% or less.
This results in higher catalytic activity even in the lower temperature range.

In particular, in the metal fine particles, it is more preferable that the first element is Ni and the second element is Re. As a result, the metal fine particles are formed of an alloy of Ni and Re, and the metal active layer 12 is further stabilized. Therefore, a hydrogen production catalyst 10 having excellent heat resistance can be obtained. In addition, high catalytic activity can be maintained for a longer period of time.

The metal fine particles may include metal fine particles formed only of the first element or metal fine particles formed only of the second element.

[Manufacturing method A1 of catalyst 10 for hydrogen production]
FIG. 3 is a flowchart showing the production method A1 of the hydrogen production catalyst 10.
Hereinafter, the production method A1 using the hydrogen production catalyst 10 will be described with reference to FIG.

(Step S101: Preparation of the substrate 11)
In step S101, the substrate 11 is prepared. FIG. 4 is a diagram showing an example of the manufacturing process of the substrate 11.

First, as shown in FIG. 4A, a flat plate-shaped metal foil 11a and a wavy metal foil 11b are prepared.
The flat metal foil 11a is obtained by rolling a metal material.
The flat wavy metal foil 11b can be obtained by processing a flat plate-shaped metal foil 11a into a wavy shape. The wavy metal foil 11b is not limited to the wave shape shown in FIG. 4A, and may have a wave shape such as a triangular wave, a rectangular wave, or a trapezoidal wave. In addition, the wave interval and wave height can be set as appropriate.

Next, as shown in FIG. 4B, the flat metal foil 11a and the wavy metal foil 11b are joined. For example, an adhesive can be used for joining the flat metal foil 11a and the wavy metal foil 11b.

Further, as shown in FIG. 4C, the joined metal foils 11a and 11b are wound around. As a result, the substrate 11 of the honeycomb structure as shown in FIG. 1 is produced.

Further, FIG. 5 is a schematic view showing an example of the substrate 11 of the hydrogen production catalyst 10. By winding only the flat metal foil 11a, the substrate 11 having a spiral structure as shown in FIG. 5 may be produced. Further, the substrate 11 is not limited to the regular spiral structure wound at equal intervals as shown in FIG. 5, and may be a distorted spiral structure wound irregularly.

(Step S102: Formation of strong acid aqueous solution layer)
In step S102, a strong acid aqueous solution layer made of a strong acid aqueous solution containing the first element is formed on the surface of the substrate 11 prepared in step S101.

First, before forming the strong acid aqueous solution layer, the substrate 11 is ultrasonically cleaned with acetone and then dried.
Next, a strong acid aqueous solution layer containing the first element is applied to the surface of the substrate 11 to form a strong acid aqueous solution layer.
The amount of the strong acid aqueous solution layer to be applied to the substrate 11 can be adjusted, for example, by adjusting the concentration of the strong acid aqueous solution, the immersion time, and the like.
The strong acid aqueous solution layer is composed of, for example, an aqueous solution of nickel (II) nitrate hexahydrate and an aqueous solution of ruthenium (III) nitrosyl chloride.

(Step S103: Drying)
In step S103, the substrate 11 on which the strong acid aqueous solution layer is formed is dried in step S102. As a result, the strong acid aqueous solution is concentrated, and a strong acid powder layer made of a powder of the strong acid (or its hydrate) of the first element is formed on the surface of the substrate 11.
Further, by repeating steps S102 and S103, the amount of the strong acid powder layer formed on the substrate 11 can be increased.
In the drying step, for example, drying can be performed in two steps. As the drying conditions, for example, in the first stage, the drying temperature is 60 ° C. and the drying time is 6 hours, and in the second stage, the drying temperature is 120 ° C. and the drying time is 6 hours.
The strong acid powder layer is composed of, for example, nickel (II) nitrate hexahydrate powder or ruthenium (III) nitrosyl nitrate powder.

(Step S104: Sintering)
In step S104, the strong acid powder layer is sintered by heating the substrate 11 on which the strong acid powder layer is formed in step S103. As a result, the strong acid powder is thermally decomposed to generate oxide fine particles having a particle size of several nm to several hundred nm. As a result, an oxide fine particle layer made of oxide fine particles of the first element is formed.
As the sintering conditions, for example, the sintering atmosphere is an air atmosphere, the sintering temperature is 400 to 600 ° C., and the sintering time is 5 to 12 hours.
The oxide fine particle layer is composed of, for example, nickel oxide metal fine particles and ruthenium oxide metal fine particles.

(Step S105: Reduction)
In step S105, the oxide fine particles of the first element are reduced by heating the substrate 11 on which the oxide fine particle layer is formed in step S104 in a reducing atmosphere. As a result, the metal fine particles of the first element are generated, and the metal active layer 12 made of the metal fine particles of the first element is formed.
As the reduction conditions, for example, the reduction atmosphere is set to a hydrogen atmosphere, the reduction temperature is set to 400 to 600 ° C, and the reduction time is set to 1 hour or more.
The metal active layer 12 is composed of, for example, Ni metal fine particles and Ru metal fine particles.

From the above, in the production method A1, a catalyst 10 for hydrogen production in which a metal active layer 12 made of metal fine particles of the first element is formed on the surface of the substrate 11 can be obtained. Further, according to the production method A1 of the present invention, the hydrogen production catalyst 10 of the present invention can be produced by a simple method without using a special device or technique.

[Manufacturing method A2 of catalyst 10 for hydrogen production]
In the method A2 for producing the hydrogen production catalyst 10, the hydrogen production catalyst 10 is produced by a method different from the production method A1 in steps S101 to S103. Steps S101'to S103' of the manufacturing method A2 described below correspond to steps S101 to S103 of the manufacturing method A1.

(Step S101': Preparation of the substrate 11)
In step S101'preparing the substrate 11, a metal foil containing Ni as a main component (hereinafter referred to as nickel foil) is used. The method for producing the substrate 11 is the same as in step S101.

(Step S102': Formation of strong acid aqueous solution layer)
In S102', the surface of the substrate 11 made of nickel foil is acid-treated to form a strong acid aqueous solution layer.
As the acid used for the acid treatment, nitric acid, sulfuric acid or the like can be used.
For example, as an acid treatment, the substrate 11 is immersed in nitric acid. As a result, nickel (II) nitrate is produced on the surface of the substrate 11 as shown in the formula (1).
Ni + 2HNO ₃ → Ni (NO ₃ ) ₂ + H ₂ … (1)
Since nickel (II) nitrate is easily soluble in water, a strong acid aqueous solution layer composed of an aqueous solution of nickel (II) nitrate is formed on the surface of the substrate 11.

(Step S103': Drying)
In step S103', the nickel foil on which the strong acid aqueous solution layer is formed in step S102' is dried. As a result, the nickel (II) nitrate aqueous solution is concentrated, and nickel (II) nitrate hexahydrate is deposited in powder form on the surface of the nickel foil. As a result, a strong acid powder layer composed of nickel (II) nitrate hexahydrate powder is formed.
As the drying conditions, for example, the drying temperature is 60 ° C. and the drying time is 6 hours.

(Steps S104, S105)
Steps S104 and S105 after step S103'are the same as the manufacturing method A1.
In step S104, the oxide fine particle layer made of nickel oxide fine particles is formed by heating the substrate 11 on which the strong acid powder layer is formed.
Subsequently, in step S105, the metal active layer 12 made of Ni metal fine particles is formed by reducing the nickel oxide fine particles.

From the above, in the production method A2, the catalyst 10 for hydrogen production in which the metal active layer 12 made of Ni metal fine particles is formed on the surface of the nickel foil can be obtained. Further, according to the production method A2 of the present invention, the hydrogen production catalyst 10 of the present invention can be produced by a simple method without using a special device or technique. Further, in the production method A2, unlike the production method A1, Ni metal fine particles can be produced by a simpler method by acid treatment without using a strong acid aqueous solution of the first element.

[Manufacturing method B1 of catalyst 10 for hydrogen production]
FIG. 6 is a flowchart showing the production method B1 of the hydrogen production catalyst 10. The production method B1 of the hydrogen production catalyst 10 further includes steps S204 and S205 different from the production method A1.
Hereinafter, steps S201 to S207 of the production method B1 using the hydrogen production catalyst 10 will be described.

(Step S201: Preparation of the substrate 11)
In step S201, the substrate 11 is prepared in the same manner as in step S101 of the manufacturing method A1.

(Step S202: Formation of first strong acid aqueous solution layer)
In step S202, the first strong acid aqueous solution layer is formed on the surface of the substrate 11 prepared in step S201 in the same manner as in step S102 of the production method A1. The first strong acid aqueous solution layer corresponds to the strong acid aqueous solution layer composed of the strong acid aqueous solution containing the first element in step S102 of the production method A1.

(Step S203: Drying 1)
In step S203, the substrate 11 on which the first strong acid aqueous solution layer is formed is dried in step S202 in the same manner as in step S103 of the production method A1. As a result, a strong acid powder layer composed of a powder of a strong acid (or a hydrate thereof) of the first element is formed.

(Step S204: Formation of a second strong acid aqueous solution layer)
In step S204, a second strong acid aqueous solution layer is further formed on the surface of the substrate 11 on which the strong acid powder layer was formed in step S203. By applying the strong acid aqueous solution containing the second element to the surface of the substrate 11, a second strong acid aqueous solution layer composed of the strong acid aqueous solution containing the second element is formed.
The second strong acid aqueous solution layer is composed of, for example, an ammonium perrhenate aqueous solution and a ruthenium (III) nitrosyl chloride aqueous solution.

(Step S205: Drying 2)
In step S205, the substrate 11 on which the second strong acid aqueous solution layer is formed is dried in step S204. As a result, the second strong acid aqueous solution is concentrated, and a strong acid powder layer composed of a powder of the second element strong acid (or its hydrate) is formed on the surface of the substrate 11. As a result, a strong acid powder layer composed of powders of the strong acid (or hydrate thereof) of the first element and the second element is formed.
The drying step is performed, for example, under the same conditions as in step S103 of the manufacturing method A1.
Examples of the strong acid powder of the second element constituting the strong acid powder layer include ammonium perrhenate powder and ruthenium (III) nitrosyl nitrate powder.
The strong acid powder layer is, for example, a strong acid powder of nickel (II) nitrate hexahydrate and ammonium perleniumate, or a strong acid powder of nickel (II) nitrate hexahydrate and ruthenium nitrosyl (III). Consists of.

(Step S206: Sintering)
In step S206, the strong acid powder layer is sintered by heating the substrate 11 on which the strong acid powder layer is formed in step S205 in the same manner as in step S104 of the manufacturing method A1. As a result, the strong acid powder composed of the first element and the second element is thermally decomposed to generate oxide fine particles of the first element and the second element. As a result, an oxide fine particle layer composed of oxide fine particles of the first element and the second element is formed.
The oxide fine particle layer is composed of, for example, oxide fine particles made of nickel oxide and rhenium oxide, and oxide fine particles made of nickel oxide and ruthenium oxide.

(Step S207: Reduction)
In step S207, similarly to step S105 of the manufacturing method A1, the substrate 11 on which the oxide fine particle layer is formed in step S206 is heated in a reducing atmosphere to obtain oxide fine particles of the first element and the second element. Give back. As a result, the metal fine particles of the first element and the second element are generated, and the metal active layer 12 made of the metal fine particles of the first element and the second element is formed. In addition, the first element and the second element can be alloyed in the heating process. As a result, the metal active layer 12 composed of the metal fine particles of the first element and the second element is formed.
The metal active layer 12 is composed of, for example, metal fine particles made of Ni and Re and metal fine particles made of Ni and Ru.

From the above, in the production method B1, a catalyst 10 for hydrogen production in which a metal active layer 12 composed of metal fine particles of the first element and the second element is formed on the surface of the substrate 11 can be obtained. Further, according to the production method B1 of the present invention, the hydrogen production catalyst 10 of the present invention can be produced by a simple method without using a special device or technique.

(Modification example)
The manufacturing method B1 is not limited to the above configuration.
For example, the formation of the first strong acid aqueous solution layer (step S202) and the formation of the second strong acid aqueous solution layer (step S204) may be interchanged.
That is, after the preparation of the substrate 11 (step S201), the second strong acid aqueous solution layer may be formed on the surface of the substrate 11 (step S204). After that, the first strong acid aqueous solution layer may be formed on the surface of the substrate 11 on which the strong acid powder layer containing the second element is formed through drying 1 (step S203) (step S202).
Further, a sintering step may be further included between the drying 1 (step S203) and the formation of the second strong acid aqueous solution layer (step S204).
That is, after the strong acid powder layer containing the first element is formed by drying 1 (step S203), the strong acid powder layer may be sintered. After that, a second strong acid aqueous solution layer may be formed on the surface of the substrate 11 on which the oxide fine particle layer containing the first element is formed by sintering (step S204).

[Manufacturing method B2 of catalyst 10 for hydrogen production]
In the production method B2 of the hydrogen production catalyst 10, the steps S101'to S103' of the production method A2 are applied to the steps S201 to S203 of the production method B1.
Steps S204 to S207 are performed in the same manner as in the manufacturing method B1.

From the above, in the production method B2, a hydrogen production catalyst 10 in which a metal active layer 12 composed of metal fine particles of Ni and a second element is formed on the surface of a nickel foil can be obtained. Further, according to the production method A2 of the present invention, the hydrogen production catalyst 10 of the present invention can be produced by a simple method without using a special device or technique. Further, in the production method B2, unlike the production method B1, Ni metal fine particles can be produced by a simpler method by acid treatment without using a strong acid aqueous solution of the first element.

[Hydrogen production device 100]
(overall structure)
FIG. 7 is a schematic diagram of a hydrogen production apparatus 100 using a hydrogen production catalyst 10.
The hydrogen production device 100 is typically a fixed-bed flow catalytic reaction device. The hydrogen production apparatus 100 includes a supply unit 101 and a catalytic reaction unit 102.
In the hydrogen production catalyst 100, the catalyst capacity can be reduced and the hydrogen production apparatus 100 can be miniaturized by using the hydrogen production catalyst 10 which exhibits high catalytic activity in a small amount.
The hydrogen production apparatus 100 is not limited to the configuration described below.

(Supply unit 101)
The supply unit 101 supplies the mixed gas required for the reaction to the catalytic reaction unit 102.
The supply unit 101 has an evaporator 103, and the water storage unit 104 has a pump 105 and a weight scale 106.

The water storage unit 104 stores water that is a raw material for steam. The water accommodating portion 104 is connected to the evaporator 103 via the pump 105.
The pump 105 pumps the water sent from the water accommodating unit 104 to the evaporator 103.
The evaporator 103 is connected to a cylinder (not shown). Further, the evaporator 103 is connected to the catalytic reaction unit 102. The evaporator 103 converts water into steam.
The evaporator 103 supplies a mixed gas containing the gas supplied from the cylinder and water vapor to the catalytic reaction unit 102. The components of the gas supplied from the cylinder are methane, nitrogen, and hydrogen, and the supply amount of each component can be adjusted as appropriate.
The weighing scale 106 measures the amount of water in the water accommodating portion 104. As a result, the amount of water supplied to the evaporator 103 can be grasped. The supply unit 101 does not have to have the weight scale 106.

(Catalyst reaction unit 102)
The catalytic reaction unit 102 includes a reaction tube 107, a hydrogen production catalyst 10, an electric furnace 109, and quartz wool 108.
Further, the catalytic reaction unit 102 may have a gas chromatograph 110, a cold trap 111, and a flow meter 112. These may be provided as an external configuration of the hydrogen production apparatus 100.

The reaction tube 107 has a cylindrical shape with a hollow inside. As shown in FIG. 7, the reaction tube 107 is arranged with the central axis direction of the cylindrical shape as the vertical direction. The upper part of the reaction tube 107 is connected to the supply unit 101. The reaction tube 107 circulates the mixed gas supplied from the supply unit 101 internally.

The hydrogen production catalyst 10 is arranged inside the reaction tube 107 and promotes a reaction to generate hydrogen.
The quartz wool 108 is arranged above and below the hydrogen production catalyst 10 arranged inside the reaction tube 107, and fixes the hydrogen production catalyst 10.
The electric furnace 109 has an electric heater and adjusts to a predetermined reaction temperature.

The gas chromatograph 110 is connected to the lower part of the reaction tube 107. The gas chromatograph 110 measures the composition of the exhaust gas discharged from the reaction tube 107.
The cold trap 111 is connected to the gas chromatograph 110. The cold trap 111 removes water vapor in the exhaust gas discharged from the reaction tube 107 via the gas chromatograph 110.
The flow meter 112 is connected to the cold trap 111. The flow meter 112 measures the flow rate of the exhaust gas discharged from the reaction tube 107 via the gas chromatograph 110 and the cold trap 111.

(Operation by hydrogen production device 100)
First, by introducing hydrogen into the catalyst reaction unit 102, the hydrogen production catalyst 10 is reduced. This step may be omitted as appropriate.
Then, the reaction tube 107 is adjusted to a predetermined reaction temperature by the electric furnace 109.
Next, methane and water vapor are supplied to the reaction tube 107 together with an inert gas such as nitrogen as a carrier gas. As a result, hydrogen is generated by the steam reforming reaction represented by the formula (2).
CH ₄ + H ₂ O → CO + 3H ₂ … (2)
Further, at the same time as the steam reforming reaction, the shift reaction represented by the formula (3) proceeds.
CO + H ₂ O → CO ₂ + H ₂ … (3)
By the above reaction, hydrogen is discharged from the reaction tube 107. Hydrogen is emitted together with exhaust gas containing CO and CO ₂ products, residual methane, residual water vapor and the like.

Methane is not limited to this as long as it is a hydrogen source gas capable of producing hydrogen by a steam reforming reaction. For example, the hydrogen source gas may be a hydrocarbon compound such as ethane or propane.

As the reaction gas, the water vapor that reacts with the hydrogen raw material gas is generated by vaporizing the water in the evaporator 103 and introduced into the reaction tube 107, but the method of supplying the water vapor is not limited to this. For example, water vapor may be generated by supplying liquid water directly to the reaction tube 107.

Hereinafter, embodiments of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the scope of these Examples.

[Manufacturing of catalyst 10 for hydrogen production]
In Examples 1-1 to 1-12, Examples 2-1 and 2-2, and Comparative Example, each hydrogen production catalyst 10 was prepared by the following method.

(Examples 1-1 to 1-9 and comparative examples)
In Examples 1-1 to 1-9 and Comparative Example, a nickel foil honeycomb structure was used as the substrate 11. The nickel foil honeycomb structure had a diameter of 8 mm, a height of 10 mm, an average wall thickness of 0.03 mm, and an average cell density of 2311 cpsi.

In Examples 1-1 and 1-5, a hydrogen production catalyst 10 having a metal active layer 12 containing Ni was produced by the above production method A1.

Specifically, in Examples 1-1 and 1-5, a nickel foil honeycomb structure (base 11) that was ultrasonically washed with acetone and dried was subjected to nickel (II) nitrate hexahydrate at room temperature. It was immersed in an aqueous solution (concentration 50%) to form a nickel (II) nitrate hexahydrate aqueous solution layer. The Ni in the nickel (II) nitrate hexahydrate aqueous solution layers of Examples 1-1 and 1-5 was 5% by weight and 10% by weight, respectively, with respect to the substrate 11.
Next, the substrate 11 coated with the aqueous solution of nickel (II) nitrate hexahydrate was dried at 60 ° C. for 6 hours and then at 120 ° C. for 6 hours to remove excess solvent, and nickel (II) nitrate hexahydrate was removed. The substrate 11 was coated with Japanese powder.
Next, this was set in an electric box type furnace and sintered in air at 500 ° C. for 6 to 8 hours to convert nickel (II) nitrate hexahydrate powder into nickel oxide.
Next, the substrate 11 carrying nickel oxide was set in an electric tube furnace and reduced at 430 ° C. for 1 hour in a hydrogen atmosphere to convert nickel oxide to Ni.

In Examples 1-2 to 1-4, 1-6, 1-7, hydrogen having a metal active layer 12 containing Ni (first element) and Re (second element) having different composition ratios according to the production method B1. The production catalyst 10 was produced.

Specifically, in Examples 1-2 to 1-4, the substrate 11 carrying nickel oxide was obtained by the same procedure as in Example 1-1, and then immersed in an aqueous solution of ammonium perrhenate (concentration 5%). To form an aqueous solution layer of ammonium perrhenate. The Re in the ammonium perrhenate aqueous solution layer of Examples 1-2 to 1-4 was 0.5% by weight, 5% by weight, and 10% by weight, respectively, with respect to the substrate 11.
Next, the nickel oxide-coated substrate 11 coated with the ammonium perrhenate aqueous solution was dried at 60 ° C. for 6 hours and then at 120 ° C. for 6 hours to remove excess solvent, and the ammonium perrhenate powder and nickel oxide were used. The coated substrate 11 was used.
Next, this was set in an electric box type furnace and sintered in air at 500 ° C. for 6 to 8 hours to convert ammonium perrhenate powder into rhenium oxide.
Next, the substrate 11 carrying nickel oxide and rhenium oxide was set in an electric tube furnace and reduced at 430 ° C. for 1 hour in a hydrogen atmosphere to make nickel oxide and rhenium oxide an alloy of Ni and Re.

In Examples 1-6 and 1-7, after the substrate 11 supporting nickel oxide was obtained by the same procedure as in Example 1-5, 1% by weight and 2% by weight of Re were supported on the substrate 11. The procedure was the same as in Examples 1-2 to 1-4, except that the ammonium perrhenate aqueous solution layer was formed.

In Examples 1-8, a catalyst 10 for hydrogen production having a metal active layer 12 containing Ni (first element) and Ru (second element) was produced by the production method B1.

Specifically, in Example 1-8, the substrate 11 carrying nickel oxide was obtained in the same procedure as in Example 1-1, and then immersed in an aqueous solution of ruthenium (III) nitrosyl chloride (concentration 10%). An aqueous layer of ruthenium (III) nitrosyl nitrate was formed. At this time, Ru in the ruthenium (III) nitrate aqueous solution layer was 0.5% by weight with respect to the substrate 11.
Next, the nickel oxide-coated substrate 11 coated with an aqueous solution of ruthenium (III) nitrosyl chloride was dried at 60 ° C. for 6 hours and then at 120 ° C. for 6 hours to remove excess solvent, and the ruthenium (III) nitrosyl chloride powder was removed. And the substrate 11 coated with nickel oxide was used.
Next, this was set in an electric box type furnace and sintered in air at 500 ° C. for 6 to 8 hours to convert ruthenium (III) nitrosyl nitrate powder into ruthenium oxide. The substrate 11 carrying nickel oxide and ruthenium oxide was set in an electric tube furnace and reduced at 430 ° C. for 1 hour in a hydrogen atmosphere to make nickel oxide and ruthenium oxide an alloy of Ni and Ru.

In Examples 1-9, a hydrogen production catalyst 10 having a metal active layer 12 containing Ru was produced by the above production method A1.

Specifically, in Example 1-9, the aqueous solution layer of ruthenium (III) nitrosyl nitrate (however, however, using the aqueous solution of ruthenium (III) nitrosyl nitrate (concentration 10%) instead of the aqueous solution of nickel (II) nitrate hexahydrate was used. The amount of Ru in the aqueous solution layer of nitrosyl nitrate (III) nitrate was 2.5% by weight based on the substrate 11), but the procedure was the same as in Example 1-1.

In the comparative example, a nickel foil honeycomb structure having no metal active layer 12 was used.

Table 1 shows the composition ratio of the metal active layer 12 of the hydrogen production catalyst 10 according to the prepared Examples 1-1 to 1-9 and the weight of each composition of the metal active layer 12 per the geometric surface area of the substrate 11. Composition amount) is shown. The composition was measured by energy dispersive X-ray analysis (EDS) attached to a scanning electron microscope (SEM) described later.

(Examples 1-10-1-12)
In Examples 1-10-1-12, as the substrate 11, a metal foil having a length of 219 mm, a width of 10 mm, and a thickness of 0.03 mm was spirally wound.
In Examples 1-10, a nickel foil was used as the metal foil.
In Examples 1-11, a stainless steel foil was used as the metal foil.
In Examples 1-12, Fe-Cr-Al foil was used as the metal foil.
In Examples 1-10 to 1-12, a hydrogen production catalyst 10 having a metal active layer 12 containing Ni (first element) and Re (second element) was produced by the above production method B1.
In Examples 1-10 to 1-12, the metal active layer 12 having the same composition ratio and composition amount ratio was formed on each of the above metal foils by the same procedure as in Example 1-6.

(Examples 2-1 and 2-2)
In Examples 2-1 and 2-2 and Comparative Example, the same nickel foil honeycomb structure as in Example 1-1 was used as the substrate 11.

In Example 2-1 a catalyst 10 for hydrogen production having a metal active layer 12 containing Ni was produced by the above production method A2.

Specifically, in Example 2-1 as an acid treatment, the substrate 11 was immersed in a 10% aqueous nitric acid solution to form a nickel (II) nitrate aqueous solution layer on the surface of the substrate 11.
Next, the substrate 11 on which the nickel (II) nitrate aqueous solution layer was formed was dried at 60 ° C. for 6 hours to remove excess solvent, and the substrate 11 was coated with nickel (II) nitrate hexahydrate powder.
Next, this was set in an electric box type furnace and sintered in air at 500 ° C. for 6 to 8 hours to convert nickel (II) nitrate hexahydrate powder into nickel oxide.
Next, the substrate 11 carrying nickel oxide was set in an electric tube furnace and reduced at 430 ° C. for 1 hour in a hydrogen atmosphere to convert nickel oxide to Ni.

In Example 2-2, a hydrogen production catalyst 10 having a metal active layer 12 containing Ni (first element) and Re (second element) was produced by the above production method B2.

Specifically, in Example 2-2, after the substrate 11 supporting nickel oxide was obtained by the same procedure as in Example 2-1 the perrhenium was supported so as to support 1% by weight of Re with respect to the substrate 11. The procedure was the same as in Example 1-6 except that the ammonium acid aqueous solution layer was formed.

[Evaluation method]
(Surface observation with scanning electron microscope (SEM))
The surface of the hydrogen production catalyst 10 produced in Examples 1-1 to 1-12 and Examples 2-1 and 2-2 was observed by SEM.

(Measurement of BET specific surface area)
The BET specific surface area was measured for the hydrogen production catalysts 10 produced in Examples 1-1 to 1-12, Examples 2-1 and 2, and Comparative Examples.

(Measurement of catalytic properties by methane steam reforming reaction)
The catalyst characteristics of the hydrogen production catalyst 10 were measured using the hydrogen production apparatus 100. Here, hydrogen was produced by a methane steam reforming reaction using methane and steam.
After the methane steam reforming reaction in the reaction tube 107, the composition and flow rate of the exhaust gas containing hydrogen, residual methane and the like were measured by a gas chromatograph 110 and a flow meter 112.
From the values measured by the gas chromatograph 110 and the flow meter 112, the methane conversion rate was determined by the formula (4).
Methane conversion rate [%] = 100 × (supplied methane-residual methane) / supplied methane ... (4)
Here, the methane conversion rate means the ratio of the amount of methane that contributed to the production of hydrogen to the amount of methane supplied during the steam reforming reaction.
The catalytic properties were evaluated from the obtained methane conversion rate.

(1) Measurement of catalyst characteristics by temperature rise experiment For the hydrogen production catalyst 10 according to Examples 1-1 to 1-12, Examples 2-1 and 2, and Comparative Example, the catalyst characteristics were determined by the temperature rise experiment. It was measured.
In the measurement of the catalyst characteristics by the temperature rise experiment, the reaction temperature was raised in a predetermined range, and the composition of the product and the gas flow rate at each temperature were measured. From this, the relationship between the methane conversion rate and the reaction temperature was obtained.
In addition, each measurement was performed after holding at each temperature for a predetermined time and stabilizing the temperature.

As a pretreatment, before the steam reforming reaction was carried out, a reduction treatment was carried out at 703 K for 1 hour with a gas in which hydrogen and nitrogen were mixed.
As reaction conditions, the flow rate of methane was 10 ml (STP) / min, the flow rate of water vapor was 13.63 ml (STP) / min, and the flow rate of nitrogen was 30 ml (STP) / min.
The ratio of the number of molecules in water vapor to the number of carbon atoms in methane (steam carbon ratio: S / C) was 1.36. The space velocity of the mixed gas of methane, water vapor, and nitrogen supplied to the reaction tube 107 was 6406 h- ¹ .

In Examples 1-1 to 1-12 and Comparative Example, the reaction temperature range was 773 to 1173K. It was held at each temperature for 30 minutes at every 50 K.
In Examples 2-1 and 2-2, the reaction temperature range was set to 673 to 1173K. It was held at each temperature for 20 minutes.
In the comparative example, the reaction temperature range was set to 873 to 1173K. In the comparative example, the catalytic activity was not shown in the temperature range lower than 873K, so the reaction temperature was set to the above range.

(2) Measurement of catalyst characteristics by isothermal experiment For Examples 2-1 and 2-2, the catalyst characteristics were measured by the isothermal experiment.
The reaction temperature was kept constant at 973 K, and the composition and gas flow rate of the product after a predetermined reaction elapsed time were measured. From this, the relationship between the methane conversion rate and the elapsed reaction time was determined.
The reaction conditions were the same as in the above-mentioned temperature rise experiment, and the reaction conditions were stricter than the normal hydrogen production conditions. The reaction time was 140 minutes.

[Evaluation results]
The evaluation results of the hydrogen production catalyst 10 according to Examples 1-1-1-12, 2-1 and 2-2 and Comparative Example are shown below.

(Evaluation Results of Examples 1-1-1 to 1-9)
FIG. 8 is an SEM image of the fine structure of the surface of the hydrogen production catalyst 10 according to Example 1-7. As shown in FIG. 8, it was confirmed that a large number of metal fine particles having a particle size of 50 nm or more and 150 nm or less were formed. Similar metal fine particles were also confirmed in the hydrogen production catalyst 10 of Examples 1-1-1-6, 1-8, 1-9.

表２に示すように、実施例１−１〜１−９におけるＢＥＴ比表面積の値は、比較例におけるＢＥＴ比表面積の値と比べて、大幅に高い値を示した。実施例１−１〜１−９に係る水素製造用触媒１０では、表面積が増加しており、表面に金属微粒子が形成されていることが確認された。 Table 2 shows the measurement results of the BET specific surface area in Examples 1-1 to 1-9 and Comparative Examples.

As shown in Table 2, the values of the BET specific surface area in Examples 1-1 to 1-9 showed significantly higher values than the values of the BET specific surface area in the comparative examples. In the hydrogen production catalyst 10 according to Examples 1-1 to 1-9, it was confirmed that the surface area was increased and metal fine particles were formed on the surface.

FIG. 9 is a graph showing the catalyst characteristics of the hydrogen production catalyst 10 according to Examples 1-1 to 1 to 1-9 and Comparative Example by the temperature rise experiment. FIG. 9 also shows the calculation results of the equilibrium conversion rate of methane under the same reaction conditions. The equilibrium conversion rate is a theoretical value of the methane conversion rate when the reactions represented by the equations (2) and (3) reach equilibrium at each temperature under a constant pressure.
In Comparative Example, it was confirmed that the catalytic activity was not exhibited in the temperature region lower than 873K, whereas in Examples 1-1 to 1-9, the catalytic activity was exhibited even in the temperature region lower than 873.
Further, in Examples 1-1 to 1-9, the methane conversion rate was higher than that in the comparative example even in a low temperature region of 1073 K or less. As described above, it was confirmed that in Examples 1-1 to 1-9, higher catalytic activity can be obtained even in a low temperature region as compared with Comparative Examples.
In particular, in Examples 1-1, 1-5 composed of Ni metal fine particles and Examples 1-2-1 to 1-4, 1-6, 1-7 composed of Ni and Re metal fine particles, the methane conversion rate was 1073 K. Even in the following low temperature range, the value close to the equilibrium conversion rate was shown. Thus, in Examples 1-1-1-7, it was confirmed that higher catalytic activity can be obtained in the low temperature region.

表３に示すように、実施例１−１０〜１−１２におけるＢＥＴ比表面積の値は、比較例におけるＢＥＴ比表面積の値と比べて、大幅に高い値を示した。実施例１−１０〜１−１２に係る水素製造用触媒１０では、表面積が増加しており、基体１１の表面に金属微粒子が形成されていることが確認された。 (Evaluation Results of Examples 1-10-1 to 1-12)
Table 3 shows the measurement results of the BET specific surface area in Examples 1-10-1 to 1-12.

As shown in Table 3, the value of the BET specific surface area in Examples 1-10 to 1-12 showed a significantly higher value than the value of the BET specific surface area in the comparative example. In the hydrogen production catalyst 10 according to Examples 1-10 to 1-12, it was confirmed that the surface area was increased and metal fine particles were formed on the surface of the substrate 11.

FIG. 10 is a graph showing the catalyst characteristics of the hydrogen production catalyst 10 according to Examples 1-10-1 to 1-12 by a temperature rise experiment. FIG. 10 also shows the calculation results of the equilibrium conversion rate of methane at each reaction temperature under the same reaction conditions. In addition, FIG. 10 also shows the results of the methane conversion rate of Example 1-6 for reference.

In Examples 1-10 to 1-12, the methane conversion rate is close to the equilibrium conversion rate even in a low temperature region of 1073 K or less, as in Example 1-6 in which the substrate 11 is a honeycomb structure made of nickel foil. Indicated. From this, it was confirmed that high catalytic activity can be obtained even when the substrate 11 is a spiral structure. Further, it was confirmed that high catalytic activity can be obtained even when the substrate 11 is made of a metal foil other than the nickel foil.

(Evaluation Results of Examples 2-1 and 2-2)
FIG. 11 is an SEM image of the fine structure of the surface of the substrate 11 before the reduction treatment in Example 2-1. FIG. 12 is an SEM image of the fine structure on the surface of the substrate 11 before the reduction treatment in Example 2-2.
In Example 2-1 as shown in FIG. 11, it was confirmed that the oxide fine particle layer containing Ni was formed on the substrate 11 by the acid treatment, and the particle size of the oxide fine particles was 50 nm or more and 150 nm or less. ..
In Example 2-2, as shown in FIG. 12, an oxide fine particle layer containing Ni (first element) and Re (second element) is formed, and the particle size of the oxide fine particles is 10 nm or more and 100 nm. Was confirmed. In Example 2-2, it was confirmed that the particles were further refined than the particles of the oxide fine particle layer according to Example 2-1.
It was confirmed that these particles were maintained as metal fine particles even after the reduction treatment.

表４に示すように、実施例２−１，２−２におけるＢＥＴ比表面積の値は、比較例におけるＢＥＴ比表面積の値と比べて、大幅に高い値を示した。実施例２−１，２−２に係る水素製造用触媒１０では、表面積が増加しており、基体１１の表面に金属微粒子が形成されていることが確認された。また、実施例２−２に係る水素製造用触媒１０では、実施例２−１に係る水素製造用触媒１０よりもＢＥＴ比表面積の値が大きく、さらに微細化が促進されていることが確認された。 Table 4 shows the measurement results of the BET specific surface area in Examples 2-1 and 2-2 and Comparative Examples.

As shown in Table 4, the value of the BET specific surface area in Examples 2-1 and 2-2 showed a significantly higher value than the value of the BET specific surface area in the comparative example. In the hydrogen production catalyst 10 according to Examples 2-1 and 2-2, it was confirmed that the surface area was increased and metal fine particles were formed on the surface of the substrate 11. Further, it was confirmed that the hydrogen production catalyst 10 according to Example 2-2 has a larger BET specific surface area value than the hydrogen production catalyst 10 according to Example 2-1 and further miniaturization is promoted. rice field.

FIG. 13 is a graph showing the catalyst characteristics of the hydrogen production catalyst 10 according to Examples 2-1 and 2-2 and Comparative Example by the temperature rise experiment.
In Comparative Example, it was confirmed that the catalytic activity was not exhibited in the temperature region lower than 873K, whereas in Examples 2-1 and 2-2, the catalytic activity was exhibited even in the temperature region lower than 873.
Further, in Examples 2-1 and 2-2, the methane conversion rate showed a significantly higher value than the methane conversion rate in the comparative example even in a low temperature region of 1073 K or less. As described above, it was confirmed that in Examples 2-1 and 2-2 by acid treatment, high catalytic activity can be obtained even in a low temperature region.

Further, in the hydrogen production catalyst 10 according to Example 2-1 in which the metal active layer 12 made of Ni metal fine particles was formed as a result of the catalyst characteristic measurement by the isothermal experiment, even after 140 minutes passed under severe hydrogen production conditions. , The methane conversion rate decreased by only about 10%. It was confirmed that the high methane conversion rate was maintained for a long time by forming Ni metal fine particles on the nickel foil. It is considered that this is because, for example, by making the components of the metal foil and the metal fine particles the same, it was possible to suppress the peeling of the metal active layer 12 due to the difference in the coefficient of thermal expansion.
Further, in the hydrogen production catalyst 10 according to Example 2-2 in which the metal active layer 12 composed of Ni and Re metal fine particles was formed, the methane conversion rate was reduced by only about 3%. It was confirmed that the alloying of Ni metal fine particles and Re metal fine particles improved heat resistance and maintained a high methane conversion rate for a longer period of time. It is considered that this is because, for example, the alloying of the Ni metal fine particles and the Re metal fine particles suppressed the coarsening of the metal fine particles.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and it goes without saying that various modifications can be made without departing from the gist of the present invention.

10 ... Hydrogen production catalyst 11 ... Base 11a, 11b ... Metal foil 12 ... Metal active layer 100 ... Hydrogen production equipment 101 ... Supply unit 102 ... Catalyst reaction unit 103.・ ・ Evaporator 104 ・ ・ ・ Water storage 105 ・ ・ ・ Pump 106 ・ ・ ・ Weight scale 107 ・ ・ ・ Reaction tube 108 ・ ・ ・ Quartz wool 109 ・ ・ ・ Electric furnace 110 ・ ・ ・ Gas chromatograph 111 ・ ・ ・Cold trap 112 ・ ・ ・ Flow meter

Claims (16)

With metal foil,
A metal active layer made of metal particles supported on the metal foil,
Equipped with
The metal particles are alloys composed of Ni and Re, and are made of an alloy.
The metal particles have a particle size in the range of 10 nm or more and 150 nm or less.
The metal foil is mainly composed of a material selected from the group consisting of Ni, stainless steel, and iron-based alloys.
The metal foil constitutes a honeycomb structure or a swirl structure.
A catalyst for hydrogen production that promotes the steam reforming reaction of hydrocarbon compounds selected from the group consisting of methane, ethane and propane. The catalyst for hydrogen production according to claim 1.
The content of Ni in the metal particles is 1 wt% or more and less than 100 wt%.
A catalyst for hydrogen production in which the content of Re in the metal particles is more than 0 wt% and 99 wt% or less. The catalyst for hydrogen production according to claim 2.
The content of Ni in the metal particles is 30 wt% or more and 92 wt% or less.
A catalyst for hydrogen production in which the content of Re in the metal particles is 8 wt% or more and 70 wt% or less. The catalyst for hydrogen production according to any one of claims 1 to 3.
The metal foil is a catalyst for hydrogen production containing Ni as a main component. The catalyst for hydrogen production according to any one of claims 1 to 4.
0.49m ² / G or more 5.68m ² Has a BET specific surface area in the range of / g or less
Catalyst for hydrogen production. The catalyst for hydrogen production according to any one of claims 1 to 5.
The metal particles have a particle size in the range of 10 nm or more and 100 nm or less.
Catalyst for hydrogen production. The catalyst for hydrogen production according to any one of claims 1 to 6.
A catalyst for hydrogen production that promotes the steam reforming reaction of methane. The method for producing a catalyst for hydrogen production according to any one of claims 1 to 7.
On the surface of the metal foil, a strong acid powder layer containing Re is formed following the formation of a strong acid powder layer containing Ni, or a strong acid powder layer containing Ni is formed following the formation of a strong acid powder layer containing Re. Form and
By thermally decomposing the strong acid powder layer containing Ni and the strong acid powder layer containing Re, an oxide particle layer containing Ni and Re is formed.
By reducing the oxide particle layer containing Ni and Re, the metal active layer made of the metal particles is formed.
A method for producing a catalyst for hydrogen production. The method for producing a catalyst for hydrogen production according to any one of claims 1 to 7.
A strong acid powder layer containing Ni is formed on the surface of the metal foil.
By thermally decomposing the strong acid powder layer containing Ni, an oxide particle layer containing Ni is formed.
A strong acid powder layer containing Re is formed on the oxide particle layer containing Ni, and a strong acid powder layer containing Re is formed.
By thermally decomposing the strong acid powder layer containing Re, an oxide particle layer containing Re is formed.
By reducing the oxide particle layer containing Ni and the oxide particle layer containing Re, the metal active layer made of the metal particles is formed.
A method for producing a catalyst for hydrogen production. The method for producing a catalyst for hydrogen production according to any one of claims 1 to 7.
A strong acid powder layer containing Re was formed on the surface of the metal foil.
By thermally decomposing the strong acid powder layer containing Re, an oxide particle layer containing Re is formed.
A strong acid powder layer containing Ni is formed on the oxide particle layer containing Re.
By thermally decomposing the strong acid powder layer containing Ni, an oxide particle layer containing Ni is formed.
By reducing the oxide particle layer containing Re and the oxide particle layer containing Ni, the metal active layer made of the metal particles is formed.
A method for producing a catalyst for hydrogen production. By acid-treating the surface of the metal foil containing the first metal element as a main component, a strong acid powder layer containing the first metal element is formed on the surface of the metal foil.
By thermally decomposing the strong acid powder layer containing the first metal element, an oxide particle layer containing the first metal element is formed.
A method for producing a catalyst for producing hydrogen, which forms a metal active layer containing the first metal element by reducing the oxide particle layer containing the first metal element. The method for producing a catalyst for hydrogen production according to claim 11.
The method for producing a catalyst for hydrogen production, wherein the first metal element is Ni. The method for producing a catalyst for hydrogen production according to claim 11 or 12.
A method for producing a catalyst for hydrogen production, in which the surface of the metal foil is acid-treated with nitric acid. The method for producing a catalyst for hydrogen production according to any one of claims 11 to 13.
Prior to the reduction of the oxide particle layer containing the first metal element, a strong acid salt powder layer containing a second metal element different from the first metal element is formed on the oxide particle layer containing the first metal element. death,
By thermally decomposing the strong acid powder layer containing the second metal element, an oxide particle layer containing the second metal element is formed.
By reducing the oxide particle layer containing the first metal element and the oxide particle layer containing the second metal element, a metal active layer containing the first metal element and the second metal element is formed.
A method for producing a catalyst for hydrogen production. The method for producing a catalyst for hydrogen production according to claim 14.
The second metal element is selected from one or more from Ru, Re, Mn, Mo, W, Cr, Ta, Hf, Os, Sn, Zn, La, Ce, Rh, Pt, Mg, Al, Si, and Cu. A method for producing a catalyst for hydrogen production. A supply unit for supplying a hydrogen raw material gas containing a hydrocarbon compound selected from the group consisting of methane, ethane and propane, and a reaction gas containing water vapor.
It is provided with a catalytic reaction unit that causes a steam reforming reaction by reacting the hydrogen raw material gas supplied from the supply unit with the reaction gas.
The catalyst reaction unit is a hydrogen production apparatus having the hydrogen production catalyst according to any one of claims 1 to 7.

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